Process for producing waterrepellent synthetic textiles



Paiented Dec. 7, 1943 cmreo snares- PATENT OFFICE PROGESS FOR PRODUCING WATER- REPELLENT SYNTHETIC TEXTILES Ernst Waltmann, Krefeld, Germany, assignor, by

mesne assignments, to E. L Du Pont,de Nemours and (lompany, Vt'ilmington;Del., a corporation of Delaware No Drawing. Application May 3, 1938, Serial No. 205,796. In Germany May 4, 1937 6 Claims.

This invention relates to method and means for producing water-repellent synthetic textile threads, filaments, films, skins, foils, sheets and the like, such for example as are derived from cellulose, and to the products resulting therefrom.

An object of the invention is 'to provide a simple, efiicient process by which materials productive of water-repellence may be incorporated directly in the spinning solution, preferably an aqueous spinning solution such as those employed in the cuprammonium or viscose processes for making artificial silk, etc., whereby upon extrusion of said solution and regeneration of the cellulose the resulting products obtained are inherently water-repellent and require no further.

or additional treatment to this end.

The invention comprises the novelproducts as well as the novel processes and steps of processes according to which such products are manwherein X is a halogen atom; N: is the radical of a tertiary amine whose nitrogen atom has become pentavalent by attachment to the CH2 group and atom X above shown; and Z is the radical of a compound from the group consisting of the thioalcohols, alkylamines, amide, sulfonamides, and nitrogeneous derivatives of the higher fatty acids which possess an OH group or an NH group. In all said compounds the radical Z is attached to the CH2 group shown through an oxygen, sulfur or trivalent nitrogen atom, and is free of water-solubilizing radicals.

More specifically, the water-soluble quatenary ammonium compounds of the character aforesaid, and which I have found satisfactory for the purposes-above stated may be derived by combining a volatile tertiary amine, such as pyridine or trimethylamine (see below), with a methylene halide as typified by the following:

The alpha-methyl-thioethers; R-S-CHaCI; The alpha-methyl-halide derivatives of the fatty acid amides:

The alpha-methyl-halide derivatives of the alkylamines: RNH-CHz-halide;

The alpha-methyl-halide compounds obtained from nitrogenous derivatives of the higher fatty acids whichpossess an OH group or an NH group attached to the nitrogen, for instance, the alpha-methyl-halides derived as indicated below from Amidines:

R-C-NH:

I NH Urethanes:

R-O-e-NH:

. O Hydrazides:

Ureas acylated on one side with higher fatty acid radicals:

n-e-rvn-eawm Dimethylol ureas acylated on one side with higher fatty acid radicals:

' onion R-( -N-( -NEPOHzQE Ureas acylated on oneside with radicals of higher chlorocarbonic esters:

R-O-C-NHC|-NHz and corresponding derivatives of thiourea:

R-O-fi-NH-fi-NH:

In each of the compounds aforesaid, R represents a hydrocarbon radical containing an aliphatic group of at least ten carbon atoms.

All of the above mentioned alpha-halogen methyl derivatives may be obtained by treatment of the parent compound, i. e., thioalcohol, fatty acid amide, urethane, or derivative thereof as aforesaid, with trioxymethylene and dry hydrochloric acid gasin an appropriate solvent, such as benzol, benzene, etc., the reaction product being thereafter converted into the corresponding water-soluble quaternary ammonium compoundby treatment with a volatile tertiary base, such as pyridine and its homologs. trimethylamine, triethylamine, etc., with the exception of the methylol compounds referred to which require treatment only with dry hydrochloric acid gas, although the reaction proceeds effectively if trioxymethylene is used in conjunction therewith. Compounds may be obtained from fatty acid halides of the formula, RC:O.halide by treatment thereof with hexamethylene-tetramine (CI-h) 8N4, and the reaction product converted into the corresponding quaternary ammonium compound by treatment with a tertiary base as aforesaid.

In addition to the above, the compounds resulting from condensation of compounds of the form R'.X.NH2 (where R represents an alkyl,

RNHCZOCI respectively, followed by treatment of the conversion product with tertiary bases such as those above referred to. Compounds of the form as above defined, include the amides, sulfonamides, and the alkylamines. For the quaternary ammonium compounds so obtained it is required that at least one of the radicals R or R contain an aliphatic group of at least ten carbon atoms. Before being added to the spinning solution, the quaternary ammonium compounds aforesaid are either madeinto a paste with a small quantity of water and the latter stirred into the spinning solution of viscose, etc., or the compounds are dissolved in an organic solvent, as for instance, xylol, and in this manner added to the solution.

When added to the aqueous spinning solution,- these compounds produce a slight etherization of the dissolved cellulose in accordance with reactions of which the following are representative:

N R.8.0'Hi.0.cellulose H.0NS

airmen, H0.cellulose s R.NH.CHg.O.cellulose 12.01

As examples of spinning solutions in accordance with the invention from which water-repellent products as aforesaid may be obtained by.

extrusion of the solution through the usual spinning dyes and subsequent regeneration of the cellulose, as by passage of the extruded solution into sulphuric acid, etc., I give the following: Examplel parts octadecylthiomethyl pyridinium chloride, is made into a paste with 40 parts of hot water, and added to 1000 parts of viscose solution containing 6% cellulose, mixed homogenously and spun by the process of extrusion through spinning dies and regeneration of the cellulose aforesaid. V The finished product is heated for 1 hour to 135 C. and shows in water a lesser degree of swelling and is of exceptional softness.

Example 2 12 parts of the quaternary ammonium compound obtained by conversion of trimethylamine with the methylene chloride compound derived from octadecylurethane C18H37.OCONH2, trioxymethylene, and hydrochloric acid are dissolved in 40 parts of hot water and added to 1000 parts of a viscose solution containing 6% cellulose, mixed homogeneously and spunas aforesaid. The finished product is heated for 1 hour to 135 C. and shows in water a lesser degree of swelling and is of exceptional softness.

Example 3 Example 4 20 parts of quaternary pyridinium compound, obtained by conversion of pyridine with the condensation product from hexamethylenetetramine and stearic acid chloride, are stirredinto a paste with parts of hot water, and the pastels stirred into 1000 parts of a viscose spinning solution containing 6% cellulose, homogeneously mixed and spun.

Example 5 10 parts of the quaternary ammonium com-p1: pound obtained by conversion of trimetnylamine-; with the methylene chloride compound deriveda from octadecylurethane CraI-LraOCONI-Iz, .tllOXy-T'i methylene and hydrochloric acid are dissolvecL -ini; 40 parts of hot water and added to a cuprammoe nium solution of cellulose containing 3%,cellulose. The whole is homogeneously mixed and is, spun. The precipitating bath which I prefer contains water having a temperature of 30-50 0. Thefinished product is heated for 1 hour 'to C. and shows in water, a lesser degree of and is of exceptional softness.

swelling The spinning fibers obtained in accordance with the examples given above or the articles formed from the above mentioned viscose spinning solutions, such as skins, films, foils, sheets and the like show, compared with the articles made from the customary viscose spinning solution, a lesserswelling in aqueous solution and increased waterrepellence.

Preparation of the alpha-halogen, methylthioothers from the higher thioalcohols by treatment 3 with triowmetbylene and dry hydrochloric acid, and conversion of the reaction product into the quaternary ammonium compounds by treatment with a volatile tertiary base, such as pyridine, is illustrated by the following examples.

Example 7 Dry hydrochloric acid gas H01 is introduced at ordinary temperature into a mixture containing 286 parts of octadecylthioalcohol,

CHQXOE) 1s.CH2.SH

500 parts of benzol, parts trioxymethylene, until the formation of the octadecylchlormethylthioether can be clearly recognized by the benzol solution becoming clear. The water from the reaction which accumulates on the bottom of the vessel, is run off, and the benzol and the surplus hydrochloric acid are removed in a vacuum.

The quaternary ammonium salt thereof, for example, with pyridine, is formed in the following manner: 335 parts of the octadecylchlormethylthioether are stirred with -80 parts of pyridine. The mixture solidifies immediately and the'quaternary pyridinium salt of the octadecylchormethylenethioether results:

Example 8 Dry hydrochloric acid gas HCl is introduced at ordinary temperature into a mixture containing 313 parts of octadecylurethane C1BH3'LOCONH2, 600 parts of benzol, parts of trioxymethylene, until the formation (if-the chlormethyl amido compound can be clearly recognized by the benzol solution becoming clear. The water from the reaction which accumulates on the bottom of the vessel, is run off, and the benzol, and-the surplus hydrochloric acid are removed in a vacuum.

The quaternary ammonium salt thereof, for example, with trimethylamine, is formed in the following manner: 361 parts of the chlormethylamido compound of the octadecylurethane are dissolved in 500 parts of benzine, 60 parts of trimethylamine are added. The mixture solidifies and the quaternary ammonium salt of the chlormethylamido-urethane results The following examples illustrate the conversion of the fatty acid amides, methylolamides or urethanes into quaternary ammonium com- P Example 9 Into a mixture, at a temperature of 40 -C., of 280 grams stearic acid amide,

CH3 (CH2) cc :ONHs

1500 grams of benzene, and 60 grams of trioxy- .methylene, dry hydrochloric acid gas is introduced until'the formation of the methylchlori'de compound takes place, which is easily recognizable'by the clearing-up of the benzene solution.

The reaction 'water collected at the bottom of the vessel is drained off, the benzene and the excess hydrochloric acid are driven off in a vacuum, and the methylchloride compound obtained in accordance with the above reaction, and having a melting point of about 55 C., is stirred with grams of pyridine, the final reaction to form the quaternary ammonium compound being as above indicated for the thioethers.

Example 1 0 Into a mixture, at a temperature of 40. 0., of

314 grams of stearic acid methylol amide,

CH3 (CH1) is-CONHCH2OH 140 parts of finely pulverized hexamethylene= tetramine-are stirred with 1208 parts of stearlc acid chloride CH3(CH2) ic-COCl and heated, while stirring constantly for one hour, at about C. Thereupon, 320 parts of pyridine are added, while stirring.

The following examples illustrate the formation of the quaternary ammonium compounds by condensation of the compounds of the type aforesaid with formaldehyde or trioxymethylene followed by treatment with the fatty acid chlorides or the corresponding chlorocarbonic acid or carbamic acid chlorides, and treatment of the reaction product with a tertiary base.

Example 12 850 grams of para-toluol sulfonamide,

CI-I3.CsH4.SO2.NH2

are melted with 300 grams of trioxymethylene at a temperature of 110-120 C. until the condensation product is formed, Thereupon 1500 grams of stearylohloride are added, the whole is well stirred and 400 grams of pyridine are added.

Example 13 400 grams of stearic acid amide,

CH3(CHa)1s-C0NH2 (stearamide) are melted with 85 grams of trioxy- I methylene at a temperature of 110-120 C. until the condensation product is formed. Thereupon 350 grams or stearylchloride are added and 150 rams of pyridine are added to the paste.

What I claim is: I

1. As an intermediate product, a solution for spinning water-repellent, synthetic sheets, filaments and like products, comprising an aqueous spinning solution of cellulose containing a watersoluble quaternary ammonium compound or the general formula Z-CI-Ia-Nt-X, wherein X is a halogen atom, N: is the radical of a volatile tertiary amine whose nitrogen atom has become pentavalent by attachment to the CH: group and atom X above shown, while Z is an aliphatic radical of at least 10 carbon atoms which is free of wate'r-solubilizing radicals and is attached to the CH: group above shown thru the agency of a trivalent nitrogen atom.

2. Process for producing water-repellent, synthetic sheets, filaments and the like of cellulose,-

which comprises preparing an aqueous cellulose spinning solution containing a water-soluble quaternary ammonium compound of the general formula ZCH2N:X, wherein X is a halogen atom, N: is the radical of a volatile tertiary amine whose nitrogen atom has become pentavalent by attachment to the CH2 group and atom X above shown, while Z is an aliphatic radical of at least 10 carbon atoms which is free of water-solubilizing radicals and is attached to the CH: group above shown thru the'agency of a trivalent nitrogen atom; extruding said solution thru an orifice, applying a cellulose regenerating treatment thereto, and heating the resultant product to split of! the tertiary amine represented by Na.

3. A spinning process which comprises: preparing a viscose spinning solution containing about 6% cellulose, combining therewith an aqueous paste of octadecylthiomethyl pyridinium chloride, extruding the same through an orifice,

and-applying a regenerating and heating treatment thereto.

"4. Process for producing water-repellent, synthetic sheets, filaments and the like of cellulose, which comprises: preparing a cellulose spinning solution containing a compound having an aliphatic radical of at least ten carbon atoms linked to the group NCI-IaNaha1id8 where N: is a tertiary amine, extruding said-solution through an orifice and-applying a cellulose regenerating treatment thereto.

5. A spinning process which comprises; preparing a viscose spinning solution containing about 6% cellulose, admixing therewith an aqueous paste of the quaternary ammonium compound obtained from chloromethylamido-octadecylurethane combined with a tertiary amine,'extruding said spinning solution through an orifice, applying a cellulose regenerating treatment thereto, and thereafter heating to remove said combined tertiary amine. a

6. A spinning process which comprises preparing a viscose spinning solution containing about 6% cellulose, combining therewith the quaternary ammonium compound represented by the formula extruding the spinning solution thru an orifice,

applying a regenerating treatment thereto, and

heating the resultant product to split oil? pyridine.

ERNST WALTMANN.

' CERTIFICATE 0F com-amok,

Patent No. 2,555,980. Y 4 December 7, 1915.

' ERNST yminmum It is hereby certified that error'appea rs in the. printed specification of the ab v9 numbered patent requiring oo'rrection as follows Page 1, first c0lumn., line h9 io r "quaternary": read '--qu aternary-; page 5, second column,

line 29, before "grams" first occurrence, insert --15OO and that the said Letters'Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.-

Signed andsealed this day of" 5;1,' A, 191 1;,

. v Leslie Frazer (Seal) Acting ComrRissioner of Patente. 

